Ammonia detection and monitoring with photofragmentation fluorescence

Buckley, Steven G.; Damm, Christopher; Vitovec, Wolfgang M.; Sgro, Lee Anne; Sawyer, Robert F.; Koshland, Catherine P.; Lucas, Donald

doi:10.1364/ao.37.008382

Cited by 30 publications

(21 citation statements)

References 18 publications

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“…18 Excimer laser fragmentation-fluorescence spectroscopy (ELFFS) has been used to detect toxic metals such as Pb, Cr, and Ni, 19 chlorinated hydrocarbons, 20,21 and ammonia at atmospheric pressure. 22 Alkali species have also been detected using ELFFS in pressurized boilers. 23,24 Raiche et al 25 have suggested that photofragmentation fluorescence might provide a useful diagnostic for acetylene detection in flames.…”

Section: Introductionmentioning

confidence: 99%

Detection of Hydrogen Peroxide Using Photofragmentation Laser-Induced Fluorescence

et al. 2008

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Photofragmentation laser-induced fluorescence (PF-LIF) is for the first time demonstrated to be a practical diagnostic tool for detection of hydrogen peroxide. Point measurements as well as two-dimensional (2D) measurements in free-flows, with nitrogen as bath gas, are reported. The present application of the PF-LIF technique involves one laser, emitting radiation of 266 nm wavelength, to dissociate hydrogen peroxide molecules into OH radicals, and another laser, emitting at 282.25 nm, to electronically excite OH, whose laser-induced fluorescence is detected. The measurement procedure is explained in detail and a suitable time separation between photolysis and excitation pulse is proposed to be on the order of a few hundred nanoseconds. With a separation time in that regime, recorded OH excitation scans were found to be thermal and the signal was close to maximum. The PF-LIF signal strength was shown to follow the same trend as the vapor pressure corresponding to the hydrogen peroxide liquid concentration. Thus, the PF-LIF signal appeared to increase linearly with hydrogen peroxide vapor-phase concentration. For 2D single shot measurements, a conservatively estimated value of the detection limit is 30 ppm. Experiments verified that for averaged point measurements the detection limit was well below 30 ppm.

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Section: Introductionmentioning

confidence: 99%

Detection of Hydrogen Peroxide Using Photofragmentation Laser-Induced Fluorescence

et al. 2008

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“…The electronic resonances for NH 3 are located in the vacuum ultraviolet, making it difficult to measure NH 3 using conventional laser techniques . Photofragmentation of NH 3 and subsequent NH fluorescence detection has been applied as a means to circumvent this problem . Another option is to probe the electronic resonances using two‐photon processes, which has been demonstrated with laser‐induced fluorescence, polarisation spectroscopy and four‐wave mixing techniques .…”

Section: Introductionmentioning

confidence: 99%

Non‐intrusive, in situ detection of ammonia in hot gas flows with mid‐infrared degenerate four‐wave mixing at 2.3 µm

Sahlberg

Hot

Aldén

et al. 2016

J Raman Spectroscopy

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We demonstrate non-intrusive, in situ detection of ammonia (NH 3 ) in reactive hot gas flows at atmospheric pressure using midinfrared degenerate four-wave mixing (IR-DFWM). IR-DFWM excitation scans were performed in the v 2 + v 3 and v 1 + v 2 vibrational bands of NH 3 around 2.3 μm for gas flow temperatures of 296, 550 and 820 K. Simulations based on spectroscopic parameters from the HITRAN database have been compared with the measurements in order to identify the spectral lines, and an absorption spectrum at 296 K has also been measured to compare with the IR-DFWM spectra. The signal-to-noise ratio of the IR-DFWM measurement was found to be higher than that of the absorption measurement. Some spectral lines in the measured IR-DFWM and absorption spectra had no matching lines in the HITRAN simulation. The detection limit of NH 3 diluted in N 2 with IR-DFWM in this spectral range was estimated at 296, 550 and 820 K to be 1.36, 4.87 and 7.06 × 10 16 molecules/cm 3 . The dependence of the NH 3 IR-DFWM signal on the quenching properties of the buffer gas flow was investigated by comparing the signals for gas flows of N 2 , Ar and CO 2 with small admixtures of NH 3 . It was found that the signal dependence on buffer gas was large at room temperature but decreased at elevated temperatures. These results show the potential of IR-DFWM for detection of NH 3 in combustion environments.

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“…The PF/FD technique has shown promise for qualitative and quantitative analysis in a variety of applications, including, for example, the detection of vaporous hydrogen peroxide, 10 monitoring of gas-phase alkalis in coal plant exhaust to reduce fouling, [11][12][13][14] quantification of lead (in both particulate and vaporous form) as an environmental pollutant, 15 detection of the photochemical smog/acid rain contributing species NO 2 and NO, 16 environmental monitoring of chlorinated hydrocarbons, 17 and analysis of atmospheric ammonia. [18][19][20][21] Photofragmentation has also been used for the detection and quantification of several types of particulate species, such as the air pollutants ammonium nitrate and ammonium sulfate, 22 carbonaceous particles and soot generated by combustion, 22,23 and a variety of sodium-containing aerosol particles. [24][25][26] Like many laser spectroscopic techniques, PF/FD offers significant advantages over traditional off-line methods of chemical analysis in that it provides nearly instantaneous results with a high degree of species differentiation.…”

Section: Introductionmentioning

confidence: 99%

Excimer Laser Photofragmentation/Fragment Detection for Analysis of the Oxygenated Hydrocarbon Ethyl-3-Ethyoxypropionate: Implications for Atmospheric Monitoring

Dalyander

Hahn

2008

Appl Spectrosc

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In the present study, the use of ArF excimer laser photofragmentation/fragment detection (PF/FD) is considered for the characterization of gaseous ethyl-3-ethyoxypropionate (EEP), a representative solvent within the class of oxygenated volatile organic compounds (VOCs). PF/FD measurements of EEP resulted in identification of the resulting photofragments as C2 and CH, allowing photofragmentation pathways to be proposed for the parent molecule for the first time. In addition, PF/PD measurements of EEP recorded in the presence of sodium-based aerosol particles resulted in a reduced signal from the EEP, indicating adsorption onto the particulates, thereby demonstrating proof-of-concept that PF/FD can be used to study heterogeneous chemical reactions relevant to atmospheric chemistry. Finally, both time-integrated and time-resolved measurements of the EEP photofragmentation signal in varying concentrations of oxygen revealed that oxygen effectively acts as a dynamic quencher of the EEP signal. In consideration of oxygen quenching, care must be taken in calibrating/analyzing data in selected applications of PF/FD for VOC characterization (such as combustion emission monitoring) in order to account for the potential variability of oxygen concentration.

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Ammonia detection and monitoring with photofragmentation fluorescence

Cited by 30 publications

References 18 publications

Detection of Hydrogen Peroxide Using Photofragmentation Laser-Induced Fluorescence

Detection of Hydrogen Peroxide Using Photofragmentation Laser-Induced Fluorescence

Non‐intrusive, in situ detection of ammonia in hot gas flows with mid‐infrared degenerate four‐wave mixing at 2.3 µm

Excimer Laser Photofragmentation/Fragment Detection for Analysis of the Oxygenated Hydrocarbon Ethyl-3-Ethyoxypropionate: Implications for Atmospheric Monitoring

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